Dye solutions thickened with borax crosslinked polygalactomannan carboxy-, hydroxy- or carbanylalkyl ethers

ABSTRACT

An improvement in fabric dyeing and printing comprising thickening cationic dye solutions with selected polygalactomannan derivatives.

United States Patent Shelso et al.

[111 ,765,832 Oct. 16, 1973 DYE SOLUTIONS THICKENED WITH BORAX CROSSLINKED POLYGALACTOMANNAN CARBOXY-, HYDROXY- OR CARBANYLALKYL ETHERS Inventors: Gerald J. Shelso; Barnabas Seaman,

both of Minneapolis, Minn.

Assignee: General Mills Chemicals, Inc., Minneapolis, Minn.

Filed: Apr. 14, 1972 Appl. No.: 244,233

u.s. Cl 8/91, 8/82, 8/85,

8/87, 8/62 Int. Cl D06p l/48 Field of Search 8/82, 83, 92, 85,

Primary Examiner-Donald Levy Attorney-Anthony A. J uettner et a1.

[5 7] ABSTRACT An improvement in fabric dyeing and printing comprising thickening cationic dye sdlutions with selected polygalactomannan derivatives.

9 Claims, No Drawings DYE SOLUTIONS THICKENED WITH BORAX CROSSLINKED POLYGALACTOMANNAN CARBOXY-, HYDROXY- OR CARBANYLALKYL ETHERS This invention relates to dyeing and printing fabric. More particularly, this invention relates to dyeing or printing fabrics using sols comprising selected derivatives of polygalactomannans as thickeners for cationic dye solutions containing borate ions.

Polygalactomannans such as guar gum and locust bean gum are excellent thickeners used for many useful purposes. The term polygalactomannan" as used herein includes the general class of polysaccharides containing both galactose and mannose units. The polygalactomannans" are usually found in the endosperm sections of leguminous seeds such as guar, locust bean, tara, honey bean, flametree and cassia occidentalis. Polygalactomannans are cross linked by the borate ion under alkaline conditions.

In the commercial dyeing or printing of fabrics dyeing of carpet tufts, space printing and other types of dyeing operations, dye solutions are thickened for the purpose of holding the dyes onto the yarn or fabric until the dye can penetrate the yarn or fabric and be set by steaming. Once the dye is set, the residual solvent and thickener are washed out of the yarn or fabric. Dyes are basically of three types, anionic dyes, nonionic dyes and cationic dyes.

The cationic dyes, sometimes called basic dyes, are those containing a cationic charge. They are usually hydrochloride, zinc chloride, oxazine chloride, ammonium chloride or quaternary ammonium chloride salts of dyes having basic groups. They are generally in concentrations of about 0.2% to 5% by weight of the sol.

These dyes have been traditionally used for dyeing animal fibers. They are also used for dyeing synthetic polymer fibers which contain anionic groups, such as modified nylon. Cationic dyes which are commercially distributed sometimes contain substantial amounts of borax, from about 10% to 85% by weight of the dye. The borax may be present as an impurity, as a result of a manufacturing technique, for purposes of improving the dispersibility of the dye, for preventing caking of the dye in powder form or for purposes of adjusting the intensity of the dye. Unmodified polygalactomannans cannot be used to thicken dye solutions containing cationic dyes because the borax present cross links the gum and forms a gel. The particular cationic dye involved is not important in respect to the cross linking of the polygalactomannans. The borax present in these dye formulations is responsible for the cross linking.

lt has now been found that selected water-soluble polygalactomannan derivatives can be used to thicken solutions containing cationic dyes formulated with borax. The polygalactomannan derivatives useful as thickeners for solutions of cationic dyes are carboxyalkyl ethers of polygalactomannan wherein the alkyl radical contains one to two carbon atoms, carbamylethyl ethers of polygalactomannan and hydroxyalkyl ethers of polygalactomannan, wherein the alkyl radical contains two to three carbon atoms. The molar substitution of the derivatives is at least about 0.1. The preferred range is about 0.1 to 1.0. The molar substitution is the average number of moles of the substitution radical per mole of anhydrohexose unit of polygalactomannan gum. The selected derivatives of the polygalactomannan are preferably used in concentrations of about 0.15 to 2% by weight of the cationic dye sol.

Carboxyalkyl ethers of polygalactomannan are commercially available. Methods of preparing carboxyalkyl ethers of polygalactomannan can be found in U.S. Pat. No. 2,520,161.

Hydroxyalkyl ethers of polygalactomannan are commercially available products. They are made by reacting polygalactomannan with alkylene oxide in the presence of an alkaline catalyst. The catalysts are in general the aluminum metal or alkaline earth metal hydroxides, such assodium, potassium or calcium hydroxides. Am- -'monia may also be used, as well as more complex basic catalysts such as benzyl trimethyl ammonium hydroxide. Very small amounts of catalyst may be employed, as low as 0.05% based on the weight of the polygalactomannan. It is generally not necessary to exceed 10% by weight of the polygalactomannan, although larger amounts might be used. In general, about 2% to 3% by weight of the polygalactomannan is employed. The reaction can be conducted at room temperature or elevated temperatures. The temperature range in which the reaction is generally conducted is about 17 to C. While higher temperatures can be used, such as up to C, there is generally no advantage achieved. The reaction can be conducted at atmospheric temperatures, under reflux, or at elevated pressures in a closed reactor. The exact pressure is not critical and while higher pressure may be employed, operation is normally conducted at whatever pressure develops during the reaction. Generally, such developed pressures will be on the order of from about 30 to 12 p.s.i.g.

The reaction may be conducted in the substantial absence of water or solvent (no water added) although the efiiciency of the reaction is very low without the addition of water. Accordingly, the reaction is generally conducted in the presence of water to provide higher reaction efficiency. In the absence of other solvents, catalytic amounts of water on the order of about 3 to 8% based on the polygalactomannan are employed. These small amounts are generally used where higher temperatures and elevated pressures are employed, whereas larger amounts of water are used when lower temperatures and atmospheric pressure is employed. Further, other organic solvents, either water-miscible or water-immiscible organic solvents, can be employed.

lllustrative of such organic solvents are isopropanol (water-miscible) and heptane (water-immiscible). Other unreactive organic solvents may be employed although the two mentioned are preferred. Such other organic solvents are the common aliphatic hydrocarbons having from five to 10 carbon atoms which are commercially available such as pentane and hexane. Alcohols higher than methanol, those having from two to six carbon atoms, may be employed also, such as tbutanol, the only requirement being that the solvent be substantially unreactive. Where higher water levels are employed, the water should be sufficient to swell the guar gum slightly, thereby making the gum more reactive. When employed with a solvent such as isopropanol or heptane, from about 10 to 80% water based on the weight of guar gum is employed. The preferred amount of water is from about 30 to 70% with the water-miscible solvents and about 20 to 30% with the water-immiscible solvents.

Where organic solvents are employed, they are generally present in an amount up to eight times the amount of gum by weight, although larger amounts may be employed, if desired. Generally, with watermiscible solvents, an amount equal to one to three times the weight of gum is employed. With waterimmiscible solvents, an amount of from three to five times the weight of gum is generally employed. With the organic solvents, the ratio by weight of water to organic solvent is preferably within the range of about 0.05 to 0.5. A range of from about 0.2 to 0.45 is preferred with the water-miscible organic solvents and from about 0.1 to 0.2 is preferred with the waterimmiscible organic solvents. In general, any unreactive, organic solvent may be employed. With the lower ratios of water to organic solvent, the reaction is. slowed. With the higher ratios, the recovery of product by filtration is slowed.

and 2,3 epoxypropyl trimethyl guar. These samples are presented as illustrations of non-resistant to cross linking polygalactomannans.

The extent of cross linking in each case was measured one hour after the alkali addition. For the measurement a grease penetrometer equipped with an aluminum cone weighing 34.7 grams and a stainless steel cone weighing 102.1 grams was used. The cones were inverted from their normal position when measuring grease. The exterior surface of the apex of the cone was attached to the arm of the penetrometer-so that the perjphery of the base of the cone contacted the crosslinked sol first. In this position the cone was allowed to free fall or sink into the sol for a period of 5 seconds. The distance of penetration was measured in 0.10 mm units. The results are shown in Table 1.

TABLE 1.RELATIVE- TOLERANCE TO BORATE ION 0.75% added borax (NBZB40'I'10H20) 5% added borax (NazB4O-10H20) Viscosity Viscosity Gum conof so]. pl; of Aluminum Steel of sol. p11 of Aluminum Steel centration before dispersion cone penecone penebefore dispersion cone penecone penem solz, borax with t-ration tration, borax with tration tratlon,

G percent added borax 1/10 mm. 1/10 in in. added borax 1/10 mm. 1/10 mm.

(luar gum l 4, 275 10. 6 44 140 3, 000 9. 3 13 30 Locust bean gum. l 3, 125 10.4 55 173 3, 200 U. 6 24 58 2.3-epoxyprpyltrnnethyl guar 1 1, 700 10.0 02 165 1, 800 9. 0 23 52 Carboxyethyl locust bean gum 1 725 10. 1 438+ 438+ 750 0. 0 438+ 438+ Carboxyethyl guar '1 Z. 000 10. 6 410 438+ 2, 075 9. 1 231 438+ Carboxymethyl guar 1 190 10. 438+ 438+ Carbamylethyl guar. 1 650 10. 4 406 438+ 900 9. 2 44 119 Hydroxyethyl guar. 1 2, 200 10. 7 105 323 2, 400 9. 7 26 52 Hydroxypropyl guar 1 3, 200 10. 6 85 296 3, 325 9. 3 37 91 Measurement not taken.

The carbamyiethyl ether of polygalactomannans As can readily be seen from the penetration data 111 made by reacting acrylamide with the polygalactoman- Table l, theunderivatized guar gum and locust bean nan in the presence of an alkaline catalyst. Lithium hydroxide is the preferred catalyst. In general, alkali metal or alkaline earth metal hydroxides, such as sodium, potassium or calcium hydroxide, can be used. Ammonia may also be used. The catalysts are usually used in amounts of about 2 to 3% by weight of the polygalactomannan. The mixture of acrylamide is added to the mixture of polygalactomannan and catalyst. Commonly, the reaction is conducted from room temperature to about 70 C. The molar ratio of acrylamide to polygalactomannan in the reaction is about 0.25 to 1.0 and usually about 0.5. The. solvent system can be the same as used in the preparation of hydroxyalkyl polygalactomannans.

The above thickeners are used in dyeing sols in amounts of about 0.15% to 0.30% by weight of the sol and in printing pastes in amounts of about 0.15% to 2%. The amount of cationic dye and borax in the sol or paste is determined by the desired intensity of the dye and the particular commerical dye formulation used.-

EXAMPLE 1 Set out below is data showing the relative effectiveness of the borax ion to cross link selected polygalactomannan derivatives.

The sols were made by dispersing the gums in the concentrations shown in Table l and borax in the concentration shown in Table l in water. The pH of the sols was adjusted to 6.8. The gums were allowed to bydrate for about 5 hours. The pH of the sols was then adjusted to the pl-is shown in Table 1 by the addition of trisodium phosphate. lncluded among the samples are underivatized guar gum, underivatized locust bean gum gum formed firm gels in the presence of borax at both borax concentrations. The carboxyalkyl ethers of the polygalactomannans remained substantially fluid at both borax concentrations. The carbamylethyl ether of polygalactomannan and the hydroxyalkyl ethers of polygalactomannan were substantially more fluid at the borax concentration level of 0.75% by weight of the gum than the polygalactomannans. At the borax concentration of 5% by weight of the gum, the sols of carbamyl ether of polygalactomannan and hydroxyalkyl ethers of polygalactomannan were still more fluid than the underivatized polygalactomannan.

EXAMPLE ll This example-illustrates the use of carboxyethyl ether of guar with a commercialcationic dye.

' Three grams of carboxyethyl ether of guar (made by using 0.5 moles acrylonitrile per 1 mole of polygalactomannan) was dispersed in one liter of water. The dispersion when slightly acidic had a viscosity of 50 centipoise. milliliters of the dispersion was added to 0.1 gram of a cationic dye. The cationic dye was Sevron Yellow R, Color Index Basic Yellow No. l1 having the following structural formula:

CH3 CH3 The dye sample contained 76.5% borate ion expressed as Na,B O-, l0H,O. The actual form of the borate ion was unknown.

The pH of the dispersion was adjusted to 8.1. No gelling occurred.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

l. A thickened cationic dye so] comprising borax, said cationic dye being in amounts of about 0.2% to 5.0% by weight of the sol and said borax being in amounts of about to 85% by weight of the cationic dye wherein the thickener is selected from carboxyalkyl ethers of polygalactomannan wherein the alkyl radical contains one to two carbon atoms, hydroxyalkyl ethers of polygalactomannan wherein the alkyl radical contains two to three carbon atoms, or carbamylethyl ethers of polygalactomannan and the molar substitution of the substituting radical is at least 0.1.

2. The composition of claim 1 wherein the thickener is in amounts of about 0.15% to 2.0% by weight of the cationic dye sol.

3. The composition of claim 1 wherein the thickener is carboxymethyl guar.

4. The composition of claim 1 wherein the thickener is carboxyethyl guar.

5. The composition of claim 1 wherein the thickener is carbamylethyl guar.

6. The composition of claim 1 wherein the thickener is carboxyethyl locust bean gum.

7. The composition of claim 1 wherein the thickener is hydroxypropyl guar.

8. The composition of claim 1 wherein the thickener is hydroxyethyl guar.

9. in the process of dyeing fabrics using a so] of a cationic dye containing borax the improvement consisting of using as the thickener a polygalactomannan derivative selected from carboxyalkyl ethers of polygalactomannan wherein the alkyl radical contains one to two carbon atoms, hydroxy alkyl ethers of polygalactomannan wherein the alkyl radical contains two to three carbon atoms, or carbamylethyl ethers of polygalactomannan, and the molar substitution of the substituting radical is at least 0.1. 

2. The composition of claim 1 wherein the thickener is in amounts of about 0.15% to 2.0% by weight of the cationic dye sol.
 3. The composition of claim 1 wherein the thickener is carboxymethyl guar.
 4. The composition of claim 1 wherein the thickener is carboxyethyl guar.
 5. The composition of claim 1 wherein the thickener is carbamylethyl guar.
 6. The composition of claim 1 wherein the thickener is carboxyethyl locust bean gum.
 7. The composition of claim 1 wherein the thickener is hydroxypropyl guar.
 8. The composition of claim 1 wherein the thickener is hydroxyethyl guar.
 9. In the process of dyeing fabrics using a sol of a cationic dye containing borax the improvement consisting of using as the thickener a polygalactomannan derivative selected from carboxyalkyl ethers of polygalactomannan wherein the alkyl radical contains one to two carbon atoms, hydroxyalkyl ethers of polygalactomannan wherein the alkyl radical contains two to three carbon atoms, or carbamylethyl ethers of polygalactomannan, and the molar substitution of the substituting radical is at least 0.1. 